Pb-Te-compounds doped with tin-antimony-tellurides for thermoelectric generators or peltier arrangements

ABSTRACT

The invention relates to a thermoelectrically active p- or n-conductive semiconductor material constituted by a compound of the general formula (I) 
 
(PbTe) 1-x (Sn 2±y Sb 2±z Te 5 ) x    (I) 
 
with 0.0001≦x≦0.5, 0≦y&lt;2 and 0≦z&lt;2, wherein 0 to 10% by weight of the compound may be replaced by other metals or metal compounds, wherein the semiconductor material has a Seebeck coefficient of at least |S|≧60 μV/K at a temperature of 25° C. and electrical conductivity of at least 150 S/cm and power factor of at least 5 μW/(cm·K 2 ), further relates to a process for the preparation of such semiconductor materials, as well as to generators and Peltier arrangements containing them.

The invention relates to Pb—Te-compounds (Pb-tellurides) doped with tin-antimony-tellurides as thermoelectrically active materials, as well as to generators and Peltier arrangements containing them.

Thermoelectric generators per se have been known for a long time, p- or n-doped semiconductors, which are heated on one side and are cooled on the other side, trans-port electrical charges through an external circuit, with electrical work being done at a load in the circuit. The efficiency achieved in this case for the conversion of heat into electrical energy is limited thermodynamically by the Carnot efficiency. For instance, with a temperature of 1000 K on the hot side and 400 K on the “cold” side, an efficiency of (1000−400):1000=60% would be possible. Unfortunately, efficiencies of only up to 10% have been achieved to date.

On the other hand, if a direct current is applied to such an arrangement, then heat will be transported from one side to the other. Such a Peltier arrangement works as a heat pump and is therefore suitable for the cooling of equipment parts, vehicles or buildings. Heating by means of the Peltier principle is also more favorable than conventional heating, because the quantity of heat transported is always greater than the conventional heat that corresponds to the energy equivalent which is supplied.

A good review of effects and materials is given e.g. by Cronin B. Vining, ITS Short Course on Thermoelectricity, Nov. 8, 1993, Yokihama, Japan.

Thermoelectric generators are currently used in space probes for the generation of direct currents, for the cathodic corrosion protection of pipelines, for the energy supply of lighted and radio buoys, and for the operation of radios and television sets. The advantages of thermoelectric generators are that they are extremely reliable, they work irrespective of atmospheric conditions such as humidity, and no material transport susceptible to disruption takes place, instead only charge transport; the fuel is burned continuously—and catalytically without a free flame—so that minor amounts of CO₁ NO_(x) and unburned fuel are released: it is possible to use any fuels from hydrogen through natural gas, gasoline, kerosene and diesel to biologically produced fuels such as rape-seed oil methyl ester.

Thermoelectric energy conversion therefore fits in extremely flexibly with future requirements such as hydrogen economy or energy production from regenerative energies.

An especially attractive application could involve use for conversion into electrical energy in electrically powered vehicles. No modification to the existing network of the fueling stations would need to be carried out. For such an application, however, efficiencies in excess of 30% would be necessary.

The conversion of solar energy directly into electrical energy could also be very attractive. Concentrators such as parabolic collectors can focus the sun's energy with efficiencies of 95-97% onto thermoelectric generators, so that electrical energy can be produced.

Higher efficiencies, however, are necessary for use as a heat pump.

It is an object of the present invention to provide thermoelectric active materials which permit higher efficiencies than previously. A characteristic of thermoelectric materials is the so-called Z factor (figure of merit). $Z = \frac{S^{2} \cdot \sigma}{K}$ with S being the Seebeck coefficient, a being the electrical conductivity and K being the thermal conductivity. The term S₂·σ is the so-called power factor and comprises all electrical parts of the thermoelectric figure of merit.

A more accurate analysis is the efficiency as η $\eta = {\frac{T_{high} - T_{low}}{T_{high}} \cdot \frac{M - 1}{M + \frac{T_{low}}{T_{high}}}}$ with M=[1+Z/2(T_(high)+T_(low))]^(1/2) (ef. Mat. Sci. and Eng. B29 (1995) 228).

The aim is therefore to provide a material having a maximally high value for Z and high achievable temperature difference. In terms of solid-state physics, many problems need to be overcome in this case:

A high a entails high electron mobility in the material; i.e. electrons (or holes in the case of p-conducting materials) must not be strongly bound to the atom rumps. Materials having a high electrical conductivity usually also have a high thermal conductivity (Wiedemann-Franz law), so that Z cannot be favorably influenced. Currently used materials such as Bi₂Te₃, PbTe or SiGe indeed represent compromises. For instance, the electrical conductivity is reduced less than the thermal conductivity by alloying. It is therefore preferable to use alloys such as e.g. (Bi₂Te₃)₉₀(Sb₂Te₃)₅(Sb₂Se₃)₅ or Bb₂Sb₂₃Te₆₅, as are described in U.S. Pat. No. 5,448,109.

For thermoelectric materials with high efficiency, it is also preferable to satisfy further constraints. Above all, they must be thermally stable so that they can work for years without substantial loss of efficiency at working temperatures of up to 1000 K. This en-tails phases which per se are stable at high temperatures, a stable phase composition, as well as negligible diffusion of alloy constituents into the adjoining contact materials and vice versa.

The recent patent literature contains descriptions of thermoelectric materials, for example U.S. Pat. No. 6,225,550 and EP-A-1 102 334. U.S. Pat. No. 6,225,550 relates essentially to materials constituted by Mg_(x)Sb_(z1) which are additionally doped with a further element, preferably a transition metal.

EP-A-1 102 334 discloses p- or n-doped semiconductor materials which represent an at least ternary material constituted by the material classes: silicides, borides, germanides, tellurides, sulfides and selenides, antimonides, plumbides and semiconducting oxides.

DE-A-101 42 624 relates. to a thermoelectric generator of Peltier arrangement having a thermoelectrically active semiconductor material constituted by a plurality of metals or metal oxides, wherein the thermoelectrically active material is selected from a p- or n-doped ternary compound as semiconductor material. Specifically, compounds of the general formula Me_(x)S^(A) _(y)S^(B) _(z) are disclosed with S^(A) _(Y)=Ge and S^(B) _(z)=Te. Lead is not disclosed as a possible metal component.

WO 20041090998 relates to new thermoelectric materials in the system Pb_(1-x)Ge_(x)Te and describes dopants to yield p- or n-doped semiconductor materials.

There is nevertheless still a need for thermoelectrically active materials which have a high efficiency and exhibit a suitable property profile for different application fields. Research in the field of thermoelectrically active materials can by no means yet be regarded as concluded, so that there is still a demand for different thermoelectric materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1/1 shows the Seebeck coefficient S for Example 1;

FIG. 1/2 shows the Seebeck coefficient S for Example 1;

FIG. 2/1 shows the Seebeck coefficient S for Example 2;

FIG. 2/2 shows the Seebeck coefficient S for Example 2;

FIG. 3/1 shows the thermal conductivity coefficient S for Example 3;

FIG. 3/2 shows the thermal diffusivity coefficient S for Example 3;

FIG. 3/3 shows the specific heat S for Example 3;

FIG. 3/4 shows the Seebeck coefficient S for Example 3;

FIG. 4/1 shows the Seebeck coefficient S for Example 4;

FIG. 4/2 shows the Seebeck coefficient S for Example 4;

FIG. 5 shows the Seebeck coefficient S for Example 5;

FIG. 6/1 shows the Seebeck coefficient S for Example 6;

FIG. 6/2 shows the Seebeck coefficient S for Example 6; and

FIG. 7 shows the Seebeck coefficient S for Example 7;

We have found that this object is achieved by a thermoelectrically active p- or n-conductive semiconductor material constituted by a compound of the general formula (I) (PbTe)_(1−x)(Sn_(2±y)Sb_(2±z)Te₅)_(x)   (I) with x value from 0.0001 to 0.5, y value from 0 to 2 and z value from 0 to 2, wherein 0 to 10% by weight of the compound may be replaced by other metals or metal compounds, wherein the semiconductor material has a Seebeck coefficient of at least |S|≧60 μV/K at a temperature of 25° C. and an electrical conductivity of at least 150 S/cm and power factor of at least 5 μW/(cm·K²) as well as a thermoelectric generator or a Peltier arrangement having this thermoelectrically active semiconductor material.

Preferably, the Seebeck coefficient is at least |S|≧80 μV/K, especially preferred at least |S|≧100 μV/K. Preferably, the electrical conductivity is at least 500 S/cm, especially preferred at least 2000 S/cm. Preferably, the material has a power factor of at least 10 μW/(cm·K²), especially preferred at least 15 μW/(cm·K²).

Preferably, in the compound of the general formula (I) x is a value from 0.0001 to 0.1, especially preferred from 0.0001 to 0.05. Particularly preferred is a value x of about 0.02. This value of 0.02 corresponds to a composition (PbTe)_(0.98)(Sn_(2±y)Sb_(2±z)Te₅)_(0.02).

In the semiconductor material according to the present invention 0 to 10% by weight, preferably 0 to 5% by weight, especially 0 to 1% by weight of the compound may be replaced by other metals or metal compounds which also may act as p- or n-dopants. Examples for other metals or metal compounds are Na, K, Mg, Mn, Fe, Co, Ni, Cu, Ag, TI, Si, Ge, As, BI, S, Se, Pb-halides, Sb-halides, Bi-halides, Sb-tellurides, 81-tellurides, and mixtures thereof.

According to one embodiment of the present invention, 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight of the compound of the general formula (I) are re-placed by dopants. These dopants are preferably selected from the group consisting of Bi, Se, Ge or As. One specific example of a dopant is Bi which is preferably employed in an amount of from 0.1 to 0.5% by weight, based on the semiconductor material. Other possible dopants are known to the person skilled in the art. The dopants and the other metals or metal compounds are selected in a way that the Seebeck coefficient, the electrical conductivity and the power factor of the material are preferably not adversely affected.

The semiconductor materials of the present invention are prepared by melting together mixtures of the element powders of the constituents or of alloys thereof for at least 1 hour and subsequently cooling the melt to a temperature which is at least 100° C. lower than the melting point of the semiconductor material. Subsequent annealing of the semiconductor material at a temperature which is at least 100° C. lower than the melting point of the semiconductor material for at least 1 hour is often beneficial.

The melting together in the first reaction stage is preferably performed for at least 2 hours, more preferably at least 5 hours, most preferably at least 10 hours. The melting together may be performed with or without mixing of the melt. For example, the melt can be mixed using a rocking furnace to ensure the composition homogeneity. The time required for the melting together is dependent on the mixing of the components. If no mixing is performed, longer times for melting together are required to obtain a homogeneous material, whereas under good mixing conditions the homogeneity is obtained after shorter hours.

Without additional mixing a typical time for melting is from 2 to 50 hours.

The melting is performed at a temperature at which at least one of the components is molten and the semiconductor material or mixture is present in a molten state. For example, the temperature is at least 900° C., preferably at least 950° C. Typically, the temperature is in the range of from 800 to 1200° C., preferably from 1000 to 1100° C.

In one embodiment of the present invention, the molten mixture is cooled at a rate of at least 50 K/h, preferably at least 100 K/h, more preferably at least 150 K/h. In another embodiment of this invention, after melting together the (homogeneous) molten mixture is rapidly cooled at a rate of at least 10 K/s, preferably at least 20 K/s, more preferably at least 100 K/s. The cooling is performed to a temperature which is at least 100 K lower than the melting point of the semiconductor material, preferably at least 200 K lower, more preferably at least 500 K lower than the melting point of the semiconductor material. In a preferred embodiment the melt is rapidly cooled to room temperature (25° C.) or lower temperatures. For example the melt can be rapidly cooled by introducing it in an ice-water mixture or into oil, liquefied N₂, liquefied NH₃, SO₂, (halogenated) alkanes or other inert liquids or gases. Other ways of rapidly cooling the melt are known to the person skilled in the art. Preferably, pressure is applied to the mixture upon cooling, e.g. from 50 to 10000 bar.

After rapidly cooling (quenching) the melt, the semiconducting material can be annealed at a temperature which is at least 100 K, preferably at least 200 K lower than the melting point of the semiconductor material. A typical temperature can be in the range of from 450 to 650° C., preferably 500 to 600° C. The annealing is performed for at least 1 hour, more preferably at least 2 hours, more preferably at least 10 hours. A typical time would be in the range of from 10 to 250 hours, more preferably 20 to 100 hours. In atypical embodiment the annealing is performed at a temperature which is 100 to 500 K lower than the melting point of the semiconductor material. A preferred temperature range is from 150 to 350 K lower than the melting point of the semiconductor material.

In a specific process, the melt is rapidly cooled at a rate of at least 20 K/s to a temperature of 25° C. or lower and the semiconductor material is subsequently annealed at a temperature which is at least 150 K lower than the melting point of the semiconductor material for at least 5 hours.

Without being bound to any theory, it is assumed that the annealing process is responsible for obtaining the high thermoelectric values in the semiconductor material of the present invention.

In a very specific embodiment the elements were reacted for one day at 1050° C. in a quartz tube. Subsequently, the quartz-tube was immediately immersed in ice water. Subsequently, the material was annealed at 550° C. for seven days.

According to the state of the art, materials like Bi₂Te3 or PbTe are produced by melting and reacting the components in a heated quartz tube. Mixing may be enhanced by rocking the heating furnace. After the reaction is completed the furnace is cooled down. Afterwards the quartz tube is removed and the thermoelectric material in the form of an ingot is cut into slices. These slices are sawn into the pieces of 3-5 mm length from which the thermoelectric module is built up.

In another technique the cooled material may be ground at ambient temperature to typical particle sizes lower than 10 μm. The ground material is pressed to parts having the desired shape. The apparent density of those pressed parts should exceed 50%, preferably 80%, of the bulk density of the material. Substances that improve the densification by pressing may be added in amounts of 0.1 to 5 Vol.-%, preferably 0.2 to 2 Vol.-% of the powdered material. Those additives must of course be inert to the thermoelectric material and vanish upon heating under inert conditions or in vacuum at temperatures below the sintering temperature. After pressing, the pressed parts are put into a sintering furnace where they are heated to a temperature up to 20 K below the melting point. Thus the pressed parts are sintered to 95% to 100% of their theoretical (bulk) density.

In order to prevent the generation of flaws or cracks by quenching the molten material it is proposed to apply processes that result in good thermal contact during the quenching procedure and, more preferred, additionally allow for quenching and application of pressure simultaneously during the cooling. In one design/embodiment of the invention the melt, staying at a temperature above the melting point, is injected into molds or cases yielding the final measures for the application, pressure die casting, a technology as it is for example used in the field of aluminum, magnesium or zinc pressure die casting. Thus the small thermoelectrically active parts are directly prepared in the right dimensions, ready to use. By this procedure the parts are quenched more rapidly than within a quartz tube because the ratio of surface that is effective for cooling compared to the volume of the parts is increased drastically compared to the case of the quartz tube. The applied pressure, preferably in the range of 10 to 1000 bars, counteracts the generation of flaws or cracks. The material is compressed on cooling and the outer layers are pressed against the core of the material. Since the volume is small com-pared to the volume of the overall ingot the absolute mechanical stresses on quenching are smaller.

It is also possible to run a continuous process by pouring the melt into a cooling channel with dimensions according to the width and height of the final parts. The material solidifies within this channel. The solidified material (in the form of a bar) is removed from the channel by a plunger and transferred into a pressing mold which smoothly covers the bar and further cools it down. This process is well known in metals processing as continuous casting. In a preferred embodiment of the invention the melt is poured into the rectangular channel that is made up between two profiled and chilled rollers. These consist of a material of high thermal conductivity.

The material is continuously quenched under increasing pressure, e.g, in the pressure range indicated above. The continuously produced bars are cut into the final parts, The present invention also relates to a semiconductor material prepared by the above process.

Furthermore, the present invention relates to a thermoelectric generator of Peltier arrangement having a thermoelectrically active p- or n-conductive semiconductor material as defined above.

The thermoelectric generators and Peltier arrangements according to the invention enhance quite generally, on the one hand, the range of available thermoelectric generators and Peltier arrangements. Owing to the different chemical systems, it is possible to satisfy different requirements in various application fields of the thermoelectric generator or Peltier arrangements. The thermoelectric generators and Peltier arrangements according to the invention hence significantly extend the possibilities for application of these elements under different conditions.

The proportion of doping elements is from 10¹⁸ to 10²⁰ charge carriers per cubic centimeter. Higher charge-carrier concentrations cause disadvantageous effects, and hence a reduced charge mobility.

A further possible way of doping is obtained if holes or electrons are deliberately introduced into the materials by means of super- or sub-stoichiometric compositions, which obviates the need for an additional doping step.

Preferably, the p- or n-doping is carried out through selection of the stoichiometric parameters y, z, and x, respectively.

The materials according to the invention are introduced into modules, as described e.g. in WO 98/44562, U.S. Pat. No. 5,448,109, EP-A-1 102 334 or U.S. Pat. No. 5,439,528, and these modules are connected in series.

The invention is further illustrated by the following examples:

EXAMPLE 1

Elemental powders in amounts corresponding to the formula (PbTe)_(1−x)(Sn₂Sb₂Te₅)_(x), x=0.01 to 0.05 (y=0, z=0), were introduced in a quartz tube. The total amount of material was about 5.2 g,

Instead of a quartz tube all other inert materials may be employed in the melting process.

Preparation: Sn₂Sb₂Te₅ was made by melting/quenching stoichiometric amounts of the elements. A mixture of PbTe and Sn₂Sb₂Te₅ (total ˜5.2 g each reaction) was heated to 950° C. over 10 h and stayed there for 6 h, followed by rocking for 1 h at the rate 5 (fast). The melts were slowly cooled to 50° C. over 24 h.

Quality of the product ingots: The obtained ingots were pretty solid but a few micro-cracks were found when they were cut. The cracks were not as serious as in the quenched ingots.

All ingots were cut to disks of approximately 5 mm thickness using a wire saw and further cut to a rectangular shape for the property measurements. A 5 mm thick disk type sample was used for characterization.

The electrical resistance was measured at room temperature with a 4-probe instrument, which is a well-known technique.

The electrical conductivity was up to 3480 S/cm.

Electrical conductivity: Sample x Conductivity 1a 0.01 3482 1b 0.02 3458 1c 0.03 2488 Conductivity/ Sample x S cm⁻¹ 1d 0.04 2381 1e 0.05 1152

The Seebeck coefficient S (thermopower) is shown in FIG. 1/1 and 1/2.

Thus, power factors in the range from 13.8 to 17.2 μW/(cm·K²) were obtained.

Power Factor: Power factor/ Sample x μW cm⁻¹ K⁻² 1a 0.01 17.2 1b 0.02 15.3 1c 0.03 13.8 1d 0.04 15.9 1e 0.05 16.8

The stoichiometric composition of Sn2Sb2Te5 created n-type materials for all doping levels. The electrical conductivities are substantially high.

EXAMPLE 2

The same process as described in example 1 was carried out for (PbTe)_(1−x)(Sn_(1.8)Sb₂Te₅)_(x), x=0.01 to 0.10.

Preparation: Sn_(1.8)Sb₂Te₅ was made by melting/quenching stoichiometric amounts of the elements. A mixture of PbTe and Sn₁₋₈Sb₂Te₅ (total ˜5.5 g each reaction) was heated to 950° C. over 10 h and stayed there for 6 h, followed by rocking for 1 h. The melts were slowly cooled to 50° C. over 24 h.

All ingots were sliced at about 5 mm thickness using a diamond blade saw and each sliced disk was cut to a rectangular shape for property measurements.

Electrical conductivity: Conductivity/ Sample X S cm⁻¹ 2a 0.01 820 2b 0.03 729 2c 0.05 237 2d 0.07 194

The Seebeck coefficient S (thermopower) is shown in FIG. 2/1 and 2/2.

Power Factor: Power factor/ Sample x μW cm⁻¹ K⁻² 2a 0.01 27.2 2b 0.03 19.1 2c 0.05 6.8 2d 0.07 6.3

The Sn_(1.8)Bb₂Te₅ at all doping levels created n-type materials. The electrical conductivities are lower than those of the materials doped with Sn₂Sb₂Te₅ and decrease as doping level increases. All materials showed twice or three times higher thermopower than the Sn₂Sb₂Te₅ doped materials of example 1.

EXAMPLE 3

High temperature thermal conductivity measurement on samples of the composition (PbTe)_(0.99)(Sn1.8Sb₂Te₅)_(0.01).

Preparation: A mixture of PbTe and Sn_(1.8)Sb₂Te₅ (total ˜125 g) was heated to 1000° C. over 10 h and then stayed there for 24 h. After being shaken several times at 1000° C., the tube was cooled to 50° C. over 10 h. The obtained ingot was cut to slices and conductivity measurements were performed.

Results at room temperature:

Electrical conductivity: 600 S/cm (several micro-pores observed)

Seebeck coefficient S (thermopower): −230.8 μV/K

Power factor: 31.9 μW/(cm·K²)

Measured thermal conductivities (see FIG. 3/1-3/3): Thermal Temperature/ Specific Heat/ Diffusivity/ conductivity/ K W s g⁻¹ K⁻¹ cm² s⁻¹ W K⁻¹ cm⁻¹ 296 0.155 0.0131 01531 323 0.155 0.0126 0.01472 373 0.156 0.0115 0.01353 473 0.157 0.0096 0.01130 573 0.158 0.0082 0.00976 673 0.158 0.0080 0.00947

The Seebeck coefficient S (thermopower) is shown in FIG. 3/4.

EXAMPLE 4

The same process as described in example 1 was carried out for (PbTe)_(1−x)(Sn_(2.2)Sb₂Te₅)_(x), x=0.01 to 0.10.

Preparation: Sn_(2.2)Sb₂Te₅ was made by melting/quenching stoichiometric amounts of the elements. A mixture of PbTe and Sn_(2.2)Sb₂Te₅ (total ˜5.5 g each reaction) was heated to 950° C. over 10 h and stayed there for 6 h, followed by rocking for 6 h. The melts were slowly cooled to 50° C. over 24 h.

All ingots were sliced to disks using a diamond blade saw and each disk was cut to a rectangular shape for property measurements.

Electrical conductivity: Conductivity/ Sample x S cm⁻¹ 4a 0.01 2153 4b 0.03 1833 4c 0.05 1336 4d 0.07 1028 4e 0.10 613

The Seebeck coefficient S (thermopower) is shown in FIG. 4/1 and 4/2.

Power Factor: Power factor/ Sample x μW cm⁻¹ K⁻² 4a 0.01 17.8 4b 0.03 12.6 4c 0.05 10.3 4d 0.07 6.9 4e 0.10 5.3

In comparison with Sn1.8Sb₂Te₅ doped materials, the electrical conductivities are higher at all doping levels and systematically decrease from 2153 to 613 S/cm as doping level increases from 0.01 to 0.10. On the other hand, thermopower shows a very small variation (82 to 93 μV/K at room temperature) at all doping levels examined.

EXAMPLE 5

The same process as described in example 1 was carried out for (PbTe)_(1−x)(Sn₂Sb_(2.2)Te₅)_(x), x=0.01 to 0.10.

Preparation: Sn₂Sb_(2.2)Te₅ was made by melting/quenching stoichiometric amounts of the elements. A mixture of PbTe and Sn₂Sb_(2.2)Te₅ (total ˜5.2 g each reaction) was heated to 1050° C. over 10 h and stayed there for 6 h, followed by rocking for 2 h. The melts were slowly cooled to 50° C. over 10 h.

All ingots were cut to disks using a diamond-blade saw and each disk was cut using a wire-blade saw to a rectangular shape for the property measurements.

Electrical conductivity: Conductivity/ Sample x S cm⁻¹ 5a 0.01 2963 5b 0.03 2844 5c 0.05 1676 5d 0.07 1150 5e 0.10 819 The Seebeck coefficient S (thermopower) is shown in FIG. 5.

Power Factor: Power factor/ Sample x μW cm⁻¹ K⁻² 5a 0.01 19.4 5b 0.03 17.2 5c 0.05 9.8 5d 0.07 8.5 5e 0.10 6.5

In comparison with (PbTe)_(1−x)(Sn_(2.2)Sb₂Te₅)_(x), the materials gained conductivity but slightly lost the thermopower, which ends up with a slight increase of power factor with the values shown above.

EXAMPLE 6

The same process as described in example 1 was carried out for (PbTe)_(1−x)(Sn_(1.5)Sb₂Te₅)_(x), x=0.01 to 0.10.

Preparation: Sn_(1.5)Sb₂Te₅ was made by melting/quenching stoichiometric amounts of the elements. A mixture of PbTe and Sn_(1.5)Sb₂Te₅ (total −5.2 g each reaction) was heated to 1050° C. over 10 h and stayed there for 6 h, followed by rocking for 2 h. The melts were slowly cooled to 50° C. over 12 h.

All ingots were sliced at about 5 mm thickness using a diamond blade saw and each sliced disk was cut to a rectangular shape for property measurements.

Electrical conductivity: Sample x Conductivity/S cm⁻¹ 6a 0.01 830 6b 0.03 558 6c 0.05 428 6d 0.07 198 6e 0.10 250

The Seebeck coefficient S (thermopower) is shown in FIG. 6/1 and 6/2.

Power Factor: Sample x Power factor/μW cm⁻¹ K⁻² 6a 0.01 19.9 6b 0.03 13.4 6c 0.05 11.2 6d 0.10 5.6

Despite the grain boundaries clearly shown in the produced ingots, the conductivities measured are moderately high and decreases as doping level increases. The thermopower of the materials with low doping level (x=0.01-0.05) are very similar.

EXAMPLE 7

The same process as described in example 1 was carried out for

(PbTe)_(1−x)(Sn₂Sb1.5Te₅)_(x), x=0.01 to 0.10.

Preparation: Sn₂Sb_(1.5)Te₅ was made by melting/quenching stoichiometric amounts of the elements. A mixture of PbTe and Sn₂Sb_(1.5)Te₅ (total ˜5.2 g each reaction) was heated to 1050° C. over 10 h and stayed there for 6 h, followed by rocking for 2 h. The melts were slowly cooled to 50° C. over 12 h.

All ingots were sliced at about 5 mm thickness using a diamond blade saw and each sliced disk was cut to a rectangular shape for property measurements.

Electrical conductivity: Sample x Conductivity/S cm⁻¹ 7a 0.01 428 7b 0.03 335 7c 0.05 221 7d 0.07 154

The Seebeck coefficient S (thermopower) is shown in FIG. 7.

Power Factor: Sample x Power factor/μW cm⁻¹ K⁻² 7a 0.01 15.8 7b 0.03 11.7 7c 0.05 9.0 7d 0.07 6.5

The Sn₂Sb_(1.5)Te₅ doped materials showed a significant decrease in the conductivity by one half compared to the Sn_(1.5)Sb₂Te₅ doped materials and the same trend of decreasing conductivity as a function of doping level. 

1. A thermoelectrically active p- or n-conductive semiconductor material constituted by a compound of the general formula (I) (PbTe)_(1−x)(Sn_(2±y)Sb_(2±z)Te₅)_(x)   (I) with 0.0001≦x≦0.5, 0≦y<2 and 0≦z<2, wherein 0 to 10% by weight of the compound may be replaced by other metals or metal compounds, wherein the semiconductor material has a Seebeck coefficient of at least |S|≧60 μV/K at a temperature of 25° C. and electrical conductivity of at least 150 S/cm and power factor of at least 5 μW/(cm·K²).
 2. A semiconductor material as claimed in claim 1, wherein the semiconductive material has a Seebeck coefficient of at least |S|≧80 μV/K, an electrical conductivity of at least 500 S/cm, and a power factor of at least 10 μW/(cm·K²).
 3. A semiconductor material as claimed in claim 1, wherein up to 10% by weight of the ternary compound of the general formula (I) are replaced by p- or n-dopants.
 4. A semiconductor material as claimed in claim 3, wherein the p- or n-dopants are selected from Na, K, Mg, Mn, Fe, Co, Ni, Cu, Ag, Tl, Si, Ge, As, Bi, S, Se, Pb-halides, Sb-halides, Bi-halides, Sb-tellurides, Bi-tellurides, and mixtures thereof.
 5. A semiconductor material as claimed in claim 1, wherein x has a value from 0.0001 to 0.05.
 6. A process for the preparation of semiconductor materials as claimed in claim 1, by melting together mixtures of the element powders of the constituents or of alloys thereof for at least 1 hour, subsequently rapidly cooling the melt to a temperature which is at least 100 K lower than the melting point of the semiconductor material, and subsequently annealing the semiconductor material at a temperature which is at least 100 K lower than the melting point of the semiconductor material, for at least 1 hour.
 7. A process as claimed in claim 6, wherein the melt is rapidly cooled at a rate of at least 50 K/s to a temperature of 25° C. or lower and the semiconductor material is subsequently annealed at a temperature which is at least 150 K lower than the melting point of the semiconductor material, for at least 5 hours.
 8. A process as claimed in claim 6, wherein pressure is applied to the mixture upon cooling.
 9. A semiconductor material prepared by a process as claimed in claim
 6. 10. A thermoelectric generator or Peltier arrangement having a thermoelectrically active p- or n-conductive semiconductor material as claimed in claim
 1. 